Process for breaking petroleum emulsions employing certain oxyalkylation products derived in turn from reactive nitrogen-containing compounds and polyepoxides



PROCESS FOR BREAKEJG PETRGLEUM EMUL- SIONS EMPLOYING CERTAIN OXYALKYLA- TION PRODUCTS DERIVED IN TURN FROM REACTIVE NITRGGEN-CONT CQM- POUNDS AND ?GLYEPOXH)ES Melvin De Groote, University City, and Kwan-Ting Sheri, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del, a corporation of Delaware No Drawing. Application August 26, 1953 Serial No. 376,763

30 Claims. (Cl. 252-344) The present invention is a continuation-in-part of our co-pending applications, Serial Nos. 305,079 (now abancloned) and 305,080 (now Patent No. 2,723,241, dated November 8, 1955), both filed August 18, 1952.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in oil emulsions by the use of products obtained by a process of oxyalkylating by means of monoepoxides, the reaction product obtained in turn by reacting certain monomeric non-resinous nitrogen-containing compounds, hereinafter described in detail, with certain phenolic polyepoxides, particularly diepoxides, also hereinafter described in detail, and congenerically associated compounds formed in their preparation.

In preparing diepoxides or the low molal polymers one does usually obtain cogeneric materials which may include monoepoxides. However, the cogeneric mixture is invariably characterized by the fact that there is on the average, based on the molecular weight of course, more than one epoxide group per molecule.

A more limited aspect of the present invention is represented by the use of the oxyalkylation products wherein the polyepoxide is represented by (1) compounds of the following formula:

and (2) cogenerically associated compounds formed in the preparation of (l) preceding, with the proviso'that it consists principallycf the monomer as distinguished from other cogeners.

Notwithstanding the fact that subsequent data will be presented in considerable detail, yet the description becomes somewhat involved and certain facts should be kept in mind. The epoxides, and particularly the diepoxides, may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative or may have a variety of connecting bridges, i. e., divalent linking radicals. Our preference is that either diphenyl 2,19,222; Patented Jan. 7, 1 958 wherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 and 1, and X is an alkyl radical containing from 1 to 4 carbon atoms.

The compounds having two oxirane rings and employed for combination with the reactive amine, such as triethanolarnine, are characterized by the following formula and cogenerically associated compounds formed in their preparation:

in which R represents a divalent radical selected from the class of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent 0 II C..

radical, the divalent sulfone radical, and the divalent monosulfide radical -S-, the divalent radical and the divalent dilsulfide radical SS-; and R 0 is the divalent radical obtained by the elimination of a in which R, R", and R' represent hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 16 carbon atoms; n represents an integer including zero and 1, and n represents a whole number not greater than 3. The above-mentioned compounds and those cogeuerically associated compounds formed in their preparation are thermoplastic and organic solvent-soluble. Reference to being thermoplastic characte'rizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings "before reacting with amine. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethylene-glycol diethylether,- diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

.The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore,-where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2 epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least,4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane (1,2-3,4 diepoxybutane) It well may be that even though the previously suggested formula represents the principal component, or compounds, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide grouper molecular and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not resins and have certain solubility characteristics not inherent in resins.

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any one of a number of mono-amines or poly-amines which are oxyalkylation-susceptible. There is available considerable literature, particularly patent literature, dealing with oxyalkylation-susceptible amines or simple derivatives thereof, such as the esters of hydroxylated amines, for instance, higher fatty acid esters of triethanolamine and the like. Reference is made to such literature for a list of a large number of suitable reactants which do not require detailed description, although a rather comprehensive number of examples appear subsequently.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and triethanolamine. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the amine to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

Such intermediate product as above noted (prior to oxyalkylation with a monoepoxide) must, in turn also be soluble but solubility is not limited to an organic solvent but may include water or, for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether one or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents the anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the factthat in many instances the preferred compounds have distinct water-solubility or are distinctly soluble in 5% acetic acid. For instance, the products freed from any solvent can be shaken with five to twenty times their weight of distilled water at ordinary temperature and are at least self-dispersing, and in many instances water-soluble, in fact, colloidally soluble. This is particularly true when there happens to be one or more nitrogen atoms present or a repetitious ether linkage as in the case of oxyethylated or oxypropylated monoamines orpolyamines.

For reasons which are obvious, the intermediate product is oxyalkylation-susceptible. It goes without saying that the final step in the process of manufacture is nothing more nor less than reacting any of the products obtained from the nitrogen-containing reactants, with ethylene oxide, propylene oxide, butylene oxide, or the like.

Similarly, the products derived by oxyalkylation with a monoepoxide can be subjected to further reaction with a product having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

, In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemicalequivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is ob- ;viously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into seven parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

in which the various characteristics have their prior significance. However, molal ratios may be varied as noted subsequently. The product thus obtained was reacted further with monoepoxide as described elsewhere,

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the prepara- 75 tion of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table H;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with suitable nitrogen-containing compounds to be employed for reaction with the polyepoxides;

Part 5 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reactions;

Part 6 is concerned with reactions involving the intermediates obtained in the manner described in Part 5, preceding, and certain alpha-beta monoepoxides having not over 4 carbon atoms;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previous described chemical compounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and 'as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a co generic mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are ither monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

it has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. Ail the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the factthat the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following struotureis preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is V V i 7 Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxide reactants.

if sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfur-containing compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of 'products, which would be unusually toxic, even though in comparatively small concentration.

PART 2' The polyepoxides and particularly the diepoxide's can be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. If a product such as bis-phenol A is employed the ultimate compound in monomeric form employed as a reactant in the present invention has the following structure:

H H H H H H ?O*% 7 0 CH3 0 Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be indicated by the following structure:

Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved in attempting to produce this compound free from cogeneric materials of related composition. The difiiculty stems from a number of sources and a few of the more important ones are as follows: i i

CHa H H H I H H 11 w iis-H O CH3 OH C1 Or i v (2) Even if one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bis-phenol A, they do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bis-phenol A nucleus by virtue of the reactive hyclroxyls present which enter into oxyalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers. Indeed, ethylene oxide can product a solid polymer. and at times apparently does, take place in connection with compounds having one, or in the present instance, two substituted oxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways it is easier to produce a poly- This same reaction can,

What has been said in regard to the theoretical aspect I example is CH3 H H H H H H 0 CH3 0 It is obvious that two moles of such material combine readily with one mole of bis-phenol A,

to produce the product which is one step further along, at least, towards polymerization. In other words, one prior example shows the reaction product obtained from one mole of the bisphenol A and two moles of epichlorohydrin. This product in turn would represent three moles of bisphenol A and four moles of epichlorohydrin.

For purpose of brevity, without going any further, the next formula is in essence one which, perhaps in an idealized way, establishes the composition of resinous products available under the name of Epon Resins as now sold in the open market. See, also, chemical pamphlet entitled Epon Surface-Coating Resins, Shell Chemical Corporation, New York city. The word Epon is a registered trademark of the Shell Chemical Corporation.

mer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone.

(4) As has been pointed out previously, monoepoxides may be present and, indeed, are almost invariably and inevitably present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one which has been indicated previously, together with the fact that in the ordinary course of reaction a diepoxide, such as may react with a mole of bis-phenol A to give a monoepoxy structure. Indeed, in the subsequent text immediately following reference is made to the dimers, trimers and tetramers in which two epoxide groups are present. Needless to say, compounds can be formed which correspond in every respect except that one terminal epoxide group is absent and in its place is a group having one chlorine atom and one hydroxyl group, or else two hydroxyl groups, or an unreacted phenolic ring.

(5) Some reference has been made to the presence of a chlorine atom and although all effort is directed towards the elimination of any chlorine-containing molecule yet it is apparent that this is often an ideal approach rather than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and a chlorine atom present. See U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech.

For the purpose of the instant invention, n may represent a number including zero, and at the most a low number such as 1, 2 or 3. This limitation does not exist in actual efforts to obtain resins as ditlerentiated from the herein described soluble materials. It is quite probable that in the resinous products as marketed for coating use the value of n is usually substantially higher. Note again what has been said previously that any formula is, at best, an over-simplification, or at the most represents perhaps only the more important or principal constituent or constituents. These materials may vary from simple non-resinous to complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups.

Referring now to what has been said previously, to wit, compounds having both an epoxy ring or the equivalent and also a hydroxyl group, one need go no further than to consider the reaction product of (17B: (|)H 53 I I t H, CH H5 1 o---opm /hi Such a compound is comparable to other compounds having both the hydroxyl and epoxy ring such as 9,10-epoxy octadecanol. The ease with which this type of compound polymerizes is pointed out by U. S. Patent No. 2,457,329, dated December 28, 1948, to Swern et al.

The same difficulty which involves the tendency to polymerize on the part of compounds having a reactive 15 ring and a hydroxyl radical may be illustrated by compounds where, instead of the oxirane ring (1,2-epoxy ring) there is present a 1,3-epoxy ring. Such compounds -are derivatives of trimethylene oxide rather than ethylene oxide. See U. S. Patents Nos. 2,462,047 and 2,462,048, both dated February 15, 1949, to Wyler.

in which R, R", and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents not over 18 carbon atoms, 11 represents an integer selected from the class of zero and l, and n' represents a whole number not greater than 3.

PART 3 Subdivision A of the aromatic nucleus, said substituent member having At the expense of repetition of what appeared previously, it may be well to recall that these materials may vary from simple soluble non-resinous to complex nonsoluble resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from convenience, reference will he made to two only, to wit, U. S. Patent 2,506,486 and U. S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidyl ethers as they are sometimes termed, are included for purpose of illustration. These particular compounds are described in the two patents just mentioned.

TABLE I 1321- Patent ample Diphenol Diglycidyl ether refernumber ence OH2 C6H4OH S Di(ep0xypr0poxyphenyl)methane 2, 506, 486 OHaCH(CeH4OH)z Di(epoxypropoxyphenyl)methylmethane.. 2, 506, 486 (CHQZO (CsH4OH): Di(epoxypropoxyphenyl)dimethylmethaue 2, 506, 48,6 CzH5C(OHa) (O6H4OH)2--. Di(epoxyprop0xyphenyl)ethylethylmethane. 2, 506, 486 (C2H5)2C (GBH4OH)2 Di(epoxypropoxyphenyl)diethylmethane 2, 506, 486 CH3O(C3H1) (CsH4OH)2 Di(epoxypropoxyphenyl)methylpropylmethane. 2, 506, 486 OH3C(C1Hs) (O@H OH)g Di(epoxypropoxyphenyl)methylphenylmethaue. 2, 506, 486 021150 (0513 (05114011); Di(ep0xypropoxypheuyl)ethylphehyhnethane. 2, 506, 486 C3H7C (O5H (G6H4OH) Digepoxypropoxyphenyl)propylphenylmethan 2, 506, 486 0413 0 (0 115) (C@H4OH) Di epoxypropoxyphenyl) butylphenylrnethane 2, 506, 486 (CHaGaHq) OH(C5H4OH): Di(epoxypropoxyphenyl)tolylmethane 2, 606, 486 (CH OaH C(CHs) (CuH4OHh. Di(epoxypropoxyphenyl)tolylmethylmethane. i 2, 506, 486 Dihydroxy diphen 4,4-bis(2,3-epoxypropoxy)diphenyl 2, 530, 353 (OH )O(O4H5.O5H3OH) 2,2-bis(4-(2,3-ep0xyprop0xy) Z-tertiarybutyl pheny1))propane 2, 530, 353

functional groups other than epoxide and hydroxyl Subdivision B groups. The former are here included, but the latter, i, highly re inou o in oluble ty e are t, As to the preparation of low-molal polymeric epoxides In summary then in light of what has been said, comor mixtures reference is made to numerous patents and pounds suitable for reaction with amines may be sumparticularly U. S. Patents Nos. 2,575,558 and 2,582,985.

marized by the following formula: To the extent that one can propose a formula, even or for greater simplicity the formula could be restated though it is an over-simplified idealization, it appears exin which the various characters have their prior significance and in which R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol III mentioned U. S. Patent No. 2,575,558. The reason is that this patent includes the same formula which has been referred to previously in Part 2, which is concerned with the theoretical aspects of diepoxide preparation. Furthermore, this formula, or its counterpart, appears in the hereto appended claims.

In light of aforementioned U. S. Patent No. 2,575,558, the following examples can be specified by reference to the formula therein provided one still bears in mind it is in essence an over-simplification.

Example R1O from HRH R n n Remarks number B19 Dibutyl phenol (ortho-para). 1G1 151 1 0,1,2 See prior notes.

B20 do H 1% 1 0,1,2 Do.

B21 Dinonylphenol(ortho-para)- E1 1% 1 0,1,2 Do.

1322 Hydroxy benzene (H) 1 0,1,2 Do.

B23 dn None 0 0,1, 2 Do.

B24 Ortho-isopropyL CH3 1 0,1,2 See prior note. As to preparation 014,4-

1 isopropylidene bis-(2-isopropylphenol) -O- see U. S. Patent No. 2,482,748, dated & Sept. 27, 1949, to Dietzler.

B25 Para-oetyl. OH:SCH5 1 0,1,2 See priornote. (As to preparation of the phenol sulfide see U. S. Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeska et a1.)

B26 Hydroxybenzene CH3 1 0,1,2 See prior note. (As to preparation of the phenol sulfide see U. 8. Patent No. l; 2,526,545.)

E l C3115 Subdivision C wherein R is a substituent selected from the class con- The prior examples have been limited largely to those slstlflg of secfmdary butyl and tertiary blltyl q lq and in which there is no divalent linking i l as in the R is a substituent selected from the class consisting of case of diphenyl compounds, or where the linking radical Y Y P Y aryl, yll and alkafyl p and i d i d f a k t ld h d ti l l a kewherein said alkyl group contains at least 3 carbon atoms. tone. Needless to say, the same procedure is employed See Patent in converting cliphenyl into a diglycidyl ether regardless H(OC2H4)90 0211mm; of the nature of the bond between the two phenolic nuclei. l I For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant. C H C H As previously pointed out the initial phenol may be 5 5 substituted, and the substituent group in turn may be a in which the -C H groups are secondary amyl groups. cyclic group such as the phenyl group or cyclohexyl group See U. S. Patent No. 2,504,064. as in the instance of cyclohexylphenol or phenylphenol. CHEM 06H Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

1 See U. S. Patent No. 2,285,563. i ar/ HO CH3 OE CHs-CCHa C (3H1 i r E CH: Similar phenols which are monofunctlonal, for instance, 1 paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be em- OH: on, ployed in reactions previously referred to, for instance, Q with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for See Patent 2,503,196- subsequent reaction with epichlorohydrin, etc.

Other samples lncludfiI OH O6 R1 ('3 B1 I R: R

wherein R is a member of the group consisting of alkyl, and alkoxy-alkyl radicals containing from 1 to 5 carbon 15* atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

aG-C-CH:

See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

(lls u CsHu 6 OH OH See U. S. Patent No. 2,331,448.

As to descriptions 'of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as Alkyl Alkyl OH OH: CH: OH

B; R1 R1 R; e

in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 As previously noted, Part 4 is concerned with the amino reactants employed in conjunction with the polyepoxide reactant usually containing two oxirane rings. Since the reactant described in detail in Part 3, preceding, is essentially an oxyalkylating agent it is obvious that any amino compound, and more broadly any nitrogen-containing compound such as an amide, which is oxyalkylation susceptible is suitable for the present purpose. In essence, this means that the product must have a labile hydrogen attached to either oxygen or nitrogen. Such hydrogen atom may be attached directly to a nitrogen atom as in the case of an amide, an amine, or the like. However, it may be attached directly to oxygen as in the case of triethanolamine; or a labile hydrogen atom in the form of a hydroxyl group may appear in the acyl radical of an amide or the ester of an amine, such as an ester of ethanoldiethyl amine; although ricinoleic acid exemplifies an acyl radical with a hydroxyl group which is somewhat reactive, yet more satisfactory, is a hydroxy carboxylic acid such as wherein R is a six-sided carbocycle of the formula C H as described in U. S. Patent No. 2,457,640, dated December 28, 1948, to Bruson et al.

One need not necessarily use monoamino compounds or compounds containing a single nitrogen atom but may use polyamino compounds including, of course, compounds where there is more "than one amide group. There is no limitation as to the group which is attached to the nitrogen atom insofar that it may be alkyl, aryl, alicyclic, and alkylaryl, arylalkyl, etc. Heterocyclic compounds such as morpholine may be employed. The amino compound or amido compound may be water-soluble or waterinsoluble. The amine may contain a phenolic hydroxyl as, for example,

where R is an alkyl group generally having five carbon atoms or more. See U. 5. Patent No. 2,410,911, dated November 12, 1946, to Wasson et a1. Further examples appear in the subsequent text.

Needless to say, since it is specified that the amino compound or amido compound be oxyalkylation susceptible it can be subjected to reaction with some other alkylene oxide than the instant reactant containing the two oxirane rings, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycide, glycidyl ethers of mathanol, ethanol, propanol, phenol, and the like. The fact that such reactants are oxyalkylation susceptible means they are also susceptible to reaction with imines, such as ethyleneimine, propyleneimine, etc. Furthermore, any non-nitrogeneous compound which is oxyalkylation susceptible, for instance, an alcohol or a phenol, may be reacted with ethylene-imine to give suitable compounds 17 to be employed as reactants in the present procedure. See, for example, U. S. Patent No. 2,318,729, dated May 11, 1943, to Wilson. This same procedure, of course, described in said Wilson patent can be used in conjunction with any alcohol or phenol. Indeed, water-soluble polymers of lower alkylene imines can be employed. See U. S. Patent No. 2,553,696, dated May 22, 1951, to Wilson. The imines may have ether linkages as previously noted. See, for example, the products described in U. S. Patent No. 2,325,514, dated July 27, 1943, to Hester.

As is obvious from what is said, one need not use organic compounds but inorganic compounds such as ammonia or hydrazine can be employed. In the case of amides, one is not limited to the amides of monocarboxy or polycarboxy acids but one may use sulfonamides or the amide of carbonic acid, i. e., urea. However, certain derivatives of urea appear more satisfactory than urea itself. See U. S. Patent No. 2,352,552, dated June 27, 1944, to Kienzle.

As to a variety of sulfonamides which are readily susceptible to oxyalkylation, particularly with ethylene oxide or propylene oxide, see U. S. Patent No. 2,577,256, dated December 4, 1951, to Lundsted. Such sulfonamide could be used as such or after treatment with one or more moles of ethylene oxide, propylene oxide, etc.

For purpose of convenience attention is directed to a sizable number of nitrogen-containing compounds which are available in the open market as differentiated from those which could be readily prepared by reaction with ethylene oxide, propylene oxide, ethyleneimine, etc. In some instances even these reactants, notwithstanding the fact that they do have a labile hydrogen atom, are more satisfactory after treatment with ethylene oxide so as to have the labile hydrogen atom attached to oxygen instead or" nitrogen.

Amine 220 (Carbide and Carbon Chemicals Company,

New York city, N. Y., designation for Amine 803 (Carbide and Carbon Chemicals Company,

New York city, N. Y., designation for Ethyl amine Diethyl amine Isopropyl amine Diisopropyl amine n-Butyl amine Dibutyl amine n-Hexyl amine Z-ethylhexyl amine Di(2-ethylhexyl) amine Ethylene Diamine Diethylene triamine Triethylene tetramine Tetraethylene pentamine Propylene diamine N-hydroxyethyl propylene diamine N,N-dihydroxyethyl ethylene diamine 2,5-dimethyl piperazine Morpholine N-hydroxyethyl morpholine N-aminoethyl morpholine N-aminopropyl morpholine Monoethanolamine Diethanolamine Triethanolamine N-methyl ethanolamine Dimethyl ethanolamine N-ethyl ethanolamine N-ethyl diethanolamine N-methyl diethanolamine 18 n-Amylamine Di-n-amylamine Sec-amylamine Diethyl ethanolamine N-butyl diethanolamine Aminoethyl ethanolamine Di(2-ethylhexyl)ethanolamine Tetraethanol ammonium hydroxide N-acetyl ethanolamine N,N-diethyl ethylene diamine Monoisopropanolamine Diisopropanolamine Triisopropanolamine Dimethyl isopropanolaniine Dibutyl isopropanolamine 1,3-diaminopropane 3-diethylaminopropylamine 1,3-diaminobutane Hexylamine Dihexylamine Heptylamine Octylamine Dioctylamine Decylamine Dodecylamine 1,3-bis-ethylaminobutane N-ethylbutylamine 2-amino-4-methylpentane 4-amino-2-butanol 1-dimethylamino-2-propano1 5-isopropylamino-l-pentanol N-butylaniline High molecular weight aliphatic amides known as Armid 8, Armid 10, Armid 12, Armid 14, Armid 16, Armid l8, Armid HT, Armid RO, Armid T, Armid TO and Armid C, as described in a chemical pamphlet entitled Armids, issued by Armour Chemical Division, Chicago 9, Illinois.

Similarly, secondary high molecular weight aliphatic amines known as Armeen 2C and Armeen ZHT, as described in circular entitled Secondary Armeens, as is sued by Armour Chemical Division, Chicago, Illinois.

Also, high molecular weight aliphatic amines known as Armeen l0, Armeen 16D, Armeen HTD, Armeen 18D, and Armeen CD, as described in a pamphlet entitled Armeens, issued by Armour Chemical Division, Armour and Company, Chicago, Illinois.

Included also are fatty diamines having both primary and secondaryamine groups and sold under the name Duomeens, such as Duomeen T, as described in a circular entitled Duomeen T issued by Armour Chemical Division, Chicago, Illinois.

Other suitable amines are primary monoamines of the type H(OC H ),,NH where 11:3 to 5.

Suitable amines having an aromatic ring include alphamethylbenzylamine, alpha methylbenzylmonoethanolamine and alphamethylbenzyl diethanolamine.

One may use tertiary alkyl primary amines such as tertiary-octylamine, alkylamine 81-R, alkylamine 81-T, a1- klyamine JMR, and alkylamine JMT. As to a description of these amines see Rohm & Haas Company, Philadelphia, Pa., pamphlet entitled Tertiary-Alkyl Primary amines.

Other amines include:

2-amino-2-methyl-1-propanol 2-amino-2-methyl-1,3-propanedio1 2-amino-2-ethyl-1,3-propanediol 3-amino-2-methy1-1-propanol Z-aminol-butanol 19 3-amino-2,2-dimethyl-1-propanol 2-amino-2,3-dimethyl-l-propanol 2,2-diethyl-2-amino ethanol 2,2-dimethyl-2-amino ethanol 3-amino-1,2-butanediol 4-amino-1,2-butanediol 2-amino-1,3-butanediol 4-amino-l ,3-butanedio1 4,4-dimethyl-1,3-butanediol- 2-amino-1,4-butanediol 3-amino-1,4-butanediol 1-amino-2,3-butanediol Tris-(hydroxy methyl) amino methane An additional desirable group of amines are dialiph'aticw aminoalkylcardanols, and particularly those having to 40 carbon atoms in the dialiphatic grouping; examples include di-2-ethylhexylamino-methylcafdanol, diamylaminomethyl cardanol, dilaurylarninorne thyl cardanol, and di-n-butylaminomethyl cardanol. See U.'S. Patent No. 2,489,672, dated November 29, 1949, to Revukas.

Further examples of this same type of material and which has available both a phenolic hydroxyl andan alkanol hydroxyl is illustrated by the condensation prod: uct derived from a phenol, either monofunctional or'difunctional, such as para-tertiary butylphenol, para-tertiary nonylphenol, and similar amylphenol, octylphenol, l phenols having a substituent such as two .butyl groups or two nonyl groups in both an orthoand the para position.

Such phenols are reacted with an aldehyde, such as formaldehyde, acetaldehyde, etc. and an alkanol phenol, such as diethanolamine, ethylethanola mine, dipropanolamine, and other amyl amines having only one amino hydrogen atom. See, for example, U. S. Patent No. 2,457,634, dated December 28, 1948, to Bond et al.

Amines having ring structures of course include aniline,-

though there are some compounds,- suchas amides, sulfonamides, urea, etc., which are much more readily oxyalkylation susceptible than acylation susceptible for the reason that it is much more difiicult to form a secondary amide, and more especially a tertiary amide, than it would be to react a primary amide with one or more moles of an alkylene oxide.

United States Patent 2,571,119, granted October 16, 1951, describes essentially the same compounds used for preparing the compositions used in practicing the present invention, and reference is made to that patent for a description of such nitrogen compounds, including imidazolines and oxyalkylated imidazolines, and their division into a number of classes.

It is to be understood that isomeric forms of the nitrogenous compounds of all 6 classes of this patent may be employed instead of the forms referred to, without departing from the invention.

Other amines,- some of which are predominantly hy- 2,396,097 and 2,552,530. Examples of hydrophile amines include glucamine and malto'sar'nine.

Particular reference is made to U. S. Patent Na 2,552,530, for the reason that it" illustrates" suitable amines in which the moleculan weight may be as high as 4,000 to 10,000. Other amines may be obtained in acomparable fashion from monoamines as raw materials PART 5 As has been pointed out previously, the reactions involved are essentialy oxyalkylation reactions involving a nitrogen-containing compound (non-resinous) having at least one'labile hydrogen atom.

Ifoneemploys a compound such as ammonia, which is a gas, the oxyalkylation procedure'can be conducted in equipment of the kind which has been described for oxyethylation, except that the procedure is reversed in that the diglycidyl ether as such is dissolved in inert solvent with or without'an added catalyst, such as 1% of sodium methylateyand is reacted by slowly passing in the reactive nitrogen-containing reactant, to' wit ammonia. However, the'most important phase of the instant invention is concerned withorganic nitrogen derivatives which are invariably solids or liquids as distinguished from gases. Therefore, the reaction with the oxyalkylating agent, i. e., the diglycidyl ether or, in any event, the polyepoxide reactant as described, is conducted in an ordinary reaction vessel which need nothave the usual modifications necessary when a gas, such as ethylene oxide, is used. Indeed, the reactions can be conducted readily in glass laboratory equipment such as the kind used for resin manufacture as described in a number of patents, as, for example, aforementioned U. S. Patent No. 2,499,365. All that is necessary is to put the reactants together and note whether the reaction goes without the presence of a catalyst. Generally speaking, if there is a basic nitrogen atom present reaction will take place. If the reaction does not take place, or takes place too slowly, then one need only repeat the experiment using a small amount of catalyst, for instance, about one, two or 3 percent of sodium methylate, or finely divided caustic soda. Any of the usual oxyalkylation catalysts can be employed. For obvious reasons, a basic catalyst is most desirable.

If the reaction proceeds too rapidly and an insoluble rubbery mass is obtained, the best procedure is simply to repeat the preparation with greater care and stop justso doing, one is well advised to react the nitrogenous re-- actant with one or more moles of ethylene oxide and then use the oxyethylated derivative instead of the initial nitrogen-containing compound. As is also known, gelation often can be prevented by introducing some other group, such as a cyclohexyl group, a phenyl group, or a long-chain aliphatic group at a pointwhere possibly there are two reactive groups immediately adjacent, as in the case of the primary amine. Actually, the choice of re actants is so wide and so diverse that this probably presents no real or additional difiiculty in the overwhelming majority of cases. p I

For purpose of convenience the following examples are included in tabular form in Table III, following. In those examples where'the reactant was 3A as described in Table I, actually there may have been comparatively small amounts of higher polymers present which were'ignored' TABLE III Ex. No.

Reactants Molar ratio Time of reaction (hrs) Max. e."

Solubility Trlethanolamine, 149.2 g. 3A, 170 g Tri-isopropanolamine, 94 g. 3A, 85 g Dihydroxyethylethylene diamine, 73 g. 3.4, 85 g Aniline, 93 g. 3A, 170 g Phenylethanolamine, 137 g.+3A, 170 g Phenyldiethanolamine, 90.5 g.+3A, 85 g Ethylphenylethauolamine, 62.5 g.+3A, 64.6 g

Diphenylamine, 84.6 g.+3A, 85 g Morpholine, 87 g.+3A, 170 g 1,3-dimethylurea, 88.1 g.+3A, 170 g Di-2-ethylhexyl ethanolamine, 142.5 g.+3A, 85 g..-

Triethanolamine+urea 1:4, +100 g., 3A, 68 g Triethanolamine-i-Propylene oxide 1:3, 161.5 g.+

Triethanolamine+ethylene oxide 1:3, 140.5 g.+

Triethanolamine+ethylene oxide 1:6, 206.5 g.+

Triethanolamine-l-propylene oxide 1:6, 248.5 g.+

Triethanolamine+ethy1ene oxide 1:9, 272.5 g.+

Triethanolamine+propylene oxide 1:9, 268.4 g.

2-aminopyridiue, 94 g.+3A, 170 g N -methyl aniline, 53.5 g.+3A, 85 g N -ethylaniline, 60.6 g.+3A, 85 g Ethyl diethanolamine, 68.5 g.+3A, 85 g See footnotes at end of table.

Brown Semi-solid.

Brownish Semi-solid.

Amber-colored hard solid.

Yellow-colored brittle ha solid.

Amber colored viscous liquid Dark amber colored liquid Dark brown liquid Dark amber solid mass Dark amber-col0red solid Amber-colored viscous liquid Wine-red viscous liquid Dark brown sticky semi-solid Dark brown semi-solid Brownish thick liquid Yellow hard solid Dark brown sticky mass Brown hard mass Brownish red thick liquid Dark amber-colored hard mass.

Yellow sticky semi-solid Dark brown thick liquid Black hard solid Amber-colored semi-solid Brown semi-solid.

Brown rubbery mass...

H20-iDSOil1biB. 5% acetic acid-soluble. Xylene-soluble. B o-insoluble. 5% acetic acidsolub1e. Xylene-soluble. HzO-insolublev 5% acetic acid-soluble. Xylene-soluble. H-,O-iusoluble. 5% acetic acid-insoluble Xylene-insoluble. Xylene GHaOH-soluble. E o-insoluble. 5% acetic acid-insoluble. Xylene-insoluble. Xylene+CHaOHsoluble. HzO-insoluble. 5% acetic acid-insoluble. Xylene-soluble. B o-insoluble. 5% acetic acid-insoluble. Xyleues0luble. E o-insoluble. 5% acetic acid-insoluble. Xylene-soluble. Elm-insoluble. 5% acetic acid-soluble. Xylene-soluble. IMO-insoluble. 5% acetic acid-insoluble. Xylene-insoluble. GENE-soluble. Ego-insoluble. {5% acetic acid-dispersiblc.

Xylene-soluble (hot). E O-insoluble. 5% acetic acid-dispersible. Xylene-soluble. HzO--1I1S0il1bl8. i5% acetic acid-dispersible.

Xylenesolub1e. HzQ-lllSOillblB. 5% acetic acids01ub1e. Xyleuesoluble. Ego-111501111316. 5% acetic acidsoluble. Xylene-soluble. Ego-insoluble. 5% acetic acid-soluble. Xylene-soluble. HzO-insoluble. 5% acetic acid-dispersible. Xylenes0lu e. HgO-iusoluble. 5% acetic aciddispersible. Xylene-soluble. HOlnso1uble. 5% acetic acid-insoluble. Xylene-insoluble. CHgOH-soluble. H 0-i.usoluble. 5% acetic acidsolub1e. Xyleneinsoluble.

yleue+ CHaOH-SOlllb19. H20S0illbl6. 5% acetic acidso1uble. Xylene-insoluble. Xylene+ CbEllaOHsolub1e.

Ego-S0111 e. 5% acetic acid-soluble.

Xylene-insoluble.

ylene+CH3OHsoluble. Hg0insoluble. 5% acetic acid-soluble. Xylene-partly soluble.

ylene+CH3OHsoluble.

5% acetic acidsoluble.

Xylenei.nsoluble.

E o-insoluble.

5% acetic acidsoluble.

Xylenepartly soluble.

ylene+CHaOH-soluble. H 0ins0luble. 5% acetic acid-soluble. Xyleneins0luble. CH3OHS0ll1b1G. EEO-insoluble.

15% acetic acid-insoluble.

Xylene-soluble. EEO-insoluble.

5% acetic acid-insoluble. Xylene-soluble. EEO-insoluble.

5% acetic acid-soluble (difficult). Xylene-soluble, partly.

TABLE III-Continued Ex. No.

Reactants Molar ratio Time of reaction (his) Max. temp., 0.

Color and physical state Solubility Butyl diethanolamine, 82.5 g.+3A, 85 g Benzylamine, 53.6 g.+3A. 85 g 2-amino-4-methyl pentane, 50.5 g. 3.4, 85 g 2-amino-2-ethyl 1,3-propanediol, 66.5 g. 4- 3A, 85 g.

z-amino-zmethyi 1,3-propanediol, 54.5 g. 3A, 85 g.

Diamylamine, 78.7 g. 3A, 85 g Nonylamine, 71.7 g. 3A, 85 g Di-2-ethyl hexylamine, 120.5 g. 314, 85 g Furfurylamine, 97 g. 3A, 170 g Tetraethanol tetraethyleue pentamine, 182.7 g.

As to nitrogen compound, see Note 1 below: 141.6

g. 3A, 51 g.

As to nitrogen compound, see Note 2 below: 206 g.

Triethanolamine Propylene oxide 1:12, 169 g.

Ttiethanolamine ethylene oxide 1:12, 135.4 5.

Triethanolamine propylene oxide 1:18, 238.6 g.

Triethanolamine ethylene oxide 1:18, 188.2 g.+

Triethanolaminc Propylene oxide 1:15, 203.8 g.

Triethanolamiue ethylene oxide 1:15, 161.8 g.+

Decyclamine 10D, 78.5 g. 3A, g

Dodecylamiue 12D, 92.5 g. 3A, 85 g Hexadecylamiue 16D, 122 g. 3A, 85 g Octadecylamine 18D, 133.5 g. 3A, 85 g P-aminophenol, 54.5 g. 3A, 85 g Beta-phenylethyl amine, 60.5 g. 3A, 85 g See footnotes at end of table.

Dark brown thick liquid.

Yellow solid Brownish solid Dark brown solid Brown solid Brown viscous liquid Yellow semi-solid Yellow viscous liquid Dark brown semi-solid Dark brown brittle solid Dark amber-colored thick fluid Dark brown thick liquid Yellow thick liquid- Dark brown thick liquid Light brown solid Black brittle solid Amber semi-solid 5% acetic acid-soluble. Xylene-partly soluble. Xylene+CH30Hsoluble. {Hm-insoluble.

{HzO-insoluble.

5% acetic acid-dispersible. Xylene-partly soluble. Xylene+OHaOH-soluble. IMO-insoluble. 5% acetic acid-dispersible. Xylene-soluble. HzO-insoluble. 5% acetic acid-soluble. Xylene-insoluble. Xylene+CHaOH-soluble. H2O-insoluble. 5% acetic acid-soluble. Xyleneinsoluble. Xylene+CHaOHso1ub1e (diificult). H 0insoluble. 5% acetic acid-insoluble. Xylene-soluble. H2Oinsoluble. 5% acetic acidi.usoluble. Xylenesolubie. Bio-insoluble. 5% acetic acidinsoluble.

ylenesoiu e. HzO-insoluble. 5% acetic aciddispersible. Xylene soluble. HzO-lIiSOlllblG. 5% acetic acid-soluble. Xyleneinsoluble. Xyleue+CH3OHsoluble. H Oinsoluble. 5% acetic acid-soluble. Xylene-insoluble. Xylene-l-CHflH-soluble. Ego-insoluble. 5% acetic acid-soluble. Xylcne-insoluble. Xylene+OH:0H-soluble. HzOdispersiblc. 5% acetic acid-soluble. Xylene-dispersible. Xylene+CHaOHsoluble. HzOdispersible. 5% acetic acidsoluble. Xylene-dispersible. Xylene+OHsOHsolubl H2Odispersible. 5% acetic acid-soluble. Xylene-dispersible. Xylcne+0Ha0Hsoluble. H2Oinsolub1e. 5% acetic acidsoluble. Xylene-soluble. Tim-insoluble. 5% acetic acid-soluble. Xylene-soluble. Ego-insoluble. 5% acetic acid-soluble. Xylene-soluble. HgOsoluble. 5% acetic acid-soluble. Xylene-soluble (partly). Xylene+CHaOH-soluble. Ego-insoluble. 5% acetic acid-soluble. Xylene-soluble. {Hm-soluble.

5% acetic ECid SOlllblG. Xylene-soluble (cloudy). Xylene+CH3OHsoluble, H 0dispersible.

5% acetic acidsoluble. Xylene-soluble. E o-soluble.

5% acetic acid-soluble. Xylenesoluble (cloudy). Xylene+CH 0Hsoluble. H2Oinsoluble.

5% acetic acidinsoluble. Xylenesoluble. H Oinsoluble.

5% acetic acid-insoluble. Xylene-soluble.

H Oinsoluble.

5% acetic acid-insoluble.

Xylenesoluble.

EEO-insoluble.

5% acetic acid-insoluble. Xylene-soluble. HzOsoluble.

5% acetic acid-soluble.

Xylene-insoluble.

{5% acetic acid-insoluble.

Xylene-soluble.

Molar Time of Max. Ex. Reactants ratio reaction temp., Color and physical state Solubility No. (hrs) C.

Ego-insoluble. G59--- Benzenesuifonyi ethyl amide, 92.6 g. 3A, 85 g-.. 2:1 s, 17s Amber thi k li uid acetic acid-insoluble.

Xylene-soluble. HBO-insoluble. G60- Benzene sulfonyl isopropyiamide, 99.6 g. 3A, 85g. 2:1 8, 0 170 do 5% acetic acid--inso1ub1e.

Xylene-soluble.

HzO-iqsoiuble I 061--- Benzene sulfonamide, 78.6 g. 3A, 85 g 2:1 2. 5 205 Dark brown solid 25 3 232333351? uble Xylene+CH 0Hs0iubIe. Hir1s01ub1e. C62 P-toluene suiionyi ethylamide, 99.7 g.+3A, 85 g--. 2:1 2, 5 190 Amb thi k liquid 5% acetic acid-insolubic.

Xylene-soluble. Hi1S0lu b1e.m b a a 06a-.- Armid 1o," 86 .+sA, 85 g 2:1 8.0 170 Brown solid g,,. gg%

Xy1ene+CH1OH-s01ubie. 5H20 i1S01u%l9.m 1 b1 ace 10 a 1 so cs4.-. Amid 14," avg-+311, 43g 2.1 8.0 175 do e Xyiene+CHa0H-so1ub1e.

H10i11s01i1 b1e.

a 06s--. Annie 16." 64.5 g.+sA, 43 21 8.0 190 Yellow solid f;ii gfi Xyiene-i-OEOH-soluble. HzO--inso1ub1e. 066.-- Triethano1amine+propy1ene oxide, 133.8 g.+3A, 2:1 5,0 175 13 m b liquid 5% acetic acid-soluble.

17 g. Xylene-soluble.

H20i.1: \s0iub1e. C67.-- Triethanoiamine+propy1ene oxide 1:27, 171.5 23 4,5 0 1 {5% acetic acid-soluble.

g.+3A, 17 g. Xy1encso1ub1e.

H2Oinso1uble. 068 Triethano1amine+propy1ene oxide 1:302, 190 2:1 4,5 1 5 do 5% acetic acid-so1ub1e.

g.+3A, 17 g. Xylene-soluble.

HzO-soiuble. C69 Triethanolemine+ethy1ene oxide 1:212, 108.2 21 4,5 190 5% acetic acid-soluble.

g.+3A, 17 g. Xyiene-l-alcohol-soluble.

t -ii 1 01 C70 Triethanolamine-i-ethylene oxide 1:243, 121.8 2;1 4,5 1 0 d 0 ace 10 am so g +3A, 17 g Xgialrligilalcohoi (1.1 mix).

H2Os( lub1 e. C71..- Triethanoiemine+ethylene oxide 1:26.13, 133.3 2:1 4.5 135 do %fggif$ jggi f%qf g 17 soluble.

130-1011111143. 1 b1 t 5 ace ic aci so u e O72 Triethanoiamme-i-ethylene oxide 1233.8, 163.6 2;1 4 5 130 y g +3A, 17 Xggialrligl-gaioohol (1.1 mix)v H20-iI 1SO1l1b18. C73..- Furfurylamine-I-propyiene oxide 1:17.19, 113.5 2;1 2,0 175 d 5% acetic acid-soluble;

g.+3A, 17 g. Xylene-soluble.

Elm-insoluble. O74 Furfmyiamine+propy1ene oxide 1:21, 131.5 g. 2;1 2.0 1 0 d 5% acetic acid-soluble.

+3.4, 17 g. Xylene-soluble.

HiOinso1ub1e. C75--. Furfury1amine+propy1ene oxide 1:24, 148.9 g. 2;1 2 1 0 5% acetic acid-soluble.

+3A, 17 g. Xylene-soluble.

Bio-insoluble. C76.-- Furfurylamine+propylene oxide 1:265, 163.4 g. z;1 2,0 195 d 5% acetic acid-soluble.

' +311, 17 g. Xylene-soluble.

HiOinso1uble. C77 Furiurylamine+propy1ene oxide 1:30.5, 186.6 21 1.0 175 d 5% acetic ac1d-so1ub1e.

g.+3A, 17 g. Xylenes01uble.

- Haw-insoluble. O78--- Furfmylamine+propylene oxide 1:513, 155 g. 2;1 1.0 135 d 5% acetic acid-soluble.

+3.4, 9 g. Xylene-soluble.

HzO-dispersible. C79--- Tetraethyiene pentamine+propylene oxide 1:243, 2:1 2 190 Dark brown thick liquid {6% acetic acid-soluble.

160 g.+3A, 17 g. Xylene-soluble. HzOdispersib1e. O80--- Diethylene triamine-l-propylene oxide 119.8, 134.4 ml 0. 5 120 Brown thi k n md {5% acetic acid-soluble.

g.+3A, 34 g. Xylene-soluble. EEO-(HSIJGTSiblB- C81.-. Diethylene triamine-i-propylene oxide 1:18.7, 118.8 2;1 0. 5 147 do 5% acetic acid-soluble.

g.+3A, 17 g. Xy1enesolubie.

Hz0dispersib1e. C82 Triethylene tetramine+propyiene oxide 1:12, 2;1 0,5 95 5% acetic acid-soluble.

85.2 g.+3A, 17 g. Xylene-soluble.

H-dispersib1e. O83 Triethylene tetramine+propylene oxide 1:19.15, 2:1 0.5 5% acetic acid-soluble.

128.4 g.+3A, 17 g. Xylene-s0iuble.

Lino-insoluble. O84... Propylene diamine-I-propyiene oxide, 1:8.5, 564 2;1 1 103 d 5% acetic acid-soluble.

g.+3A, 17 g. Xylene-soluble.

Hz0inso1uble. C85 Propylene diamine-l-propyiene oxide 1:103, 67 2:1 1 Ye115 thi k liquid 5% acetic acid-soluble.

g.+3A, 17 g. Xylene-soluble.

Eco-insoluble. C86--- Propylene diamine-l-propylene oxide 1:20, 121 21 1 100 do 5% acetic acid-so1ubie.

. g.+3A, 17 g. Xylenesoiuble.

Ego-insoluble. 087.-- Pr pylen diamine+pr0pyiene oxide 1:25, 183 2:1 1 100 do {5% acetic acid-soluble.

17 g. Xyienesolub1e.

. HzO-insoiuble. CS8 Meta-phenyiene diamine+propylene oxide 1:11.7, 2:1 1. 5 90 Dark amber thick liquid 8001510 80id'-d1SP9IS1b19- 78.6 7 g- Xylenesolub1e.

Ha0-insoiuble. C89--- M ta-ph nylene d1amin +propy1ene oxide 1:27.6, 2:1 2 100 do 5% acetic acid-dispersible, E 9 Xylene-soluble.

HzO-insolubie. 090--. eta-p eny ne d amme+propy1ene oxlde 1:43, 2:1 2 do 5% acetic acid-disperslble, 1 9 Xylene-soluble,

See footnotes at end of table.

TABLE TIL-Continued Molar Time of Max. Ex. Reactants r ratio reaction temp., Color and physical state Solubility No. (hrs.) C.

Him-insoluble. C91 Meta-phenylene diamine+propylene oxide 1:55, 2:1 2 95 Dark amber thick liquid 5% acetic acid-dispersible. 165 g.+3A, 9 g. Xy1enesoluble.

HzO-dispersible. C92... Furiurylamine+ethylene oxide+propylene oxide 2:1 .75 100 Brown thick liquid 5% acetic acid-soluble.

1:15.5:11.3, 143.4 g.-l--3A, 17 g. Xylene-soluble.

H2O-dispersible. C93..- Furturylamine+ethy1 ene oxide+propylene oxide 2:1 .75 100 do 5% acetic acidsoluble.

1:15.5:16.4, 173 g.+3A, 17 g. Y Xylene-soluble.

HzO-dispersiblti. C94.-. Furiurylamine+ethylene oxide+propylene oxide 2:1 2 140 do 5% acetic acid-soluble.

1:15.5:23.5, 214.2 g.+3A, 17 g. Xylenesoluble.

HzO-dlspersible. C95... Furturylamine+ethyiene oxide-l-propylene oxide 2:1 2 130 do 5% acetic acid-soluble.

1:15.5:32.2, 264.7 g.+3A, 17 g. Xylene-soluble.

' Ha-insoluble. C96..- Cationic amine 220, 150 g.+3A, 85 g. (See Note 3.). 2:1 3 200 Dark brown semi-solid acetic acid-soluble.

Xylene-soluble.

2% sodium methylate used as catalyst.

See previous reference to this material.

Nora 1.Obtained by reaction from 2 moles butylghenol, 2 moles formaldehyde, and 1 mole dlhydroxyethyl, ethylenediamine.

No'rn 2.Obt-ained by reaction from 1 mole amylp enol resin. 2 moles iormaldeh de, and 2 moles dicthanolamine.

No'rn 3.Amine 220 is 1-hydroxyethyl-2-heptadecenyl glyoxalidine, a product of arbide & Carbon Chemicals Corporation.

Products obtained by oxyalkylation of amines, involving either oxyethylation or oxypropylation, or both, are expressed in molal ratios of amine to alkylene oxide in this table and subsequent table of examples.

As previously pointed out one can use the product that the epoxide value, whether using pyridine hydrochlowhich is a mixture of the monomer derived from bisride dissolved in pyridine or in chloroform, is still defiphenol A and corresponding to the previous formula of: nitely lower than one would expect, indicates beyond CH1: 0H CH:

5 OH, in which n varies from 1 to 3 and, as far as is possible doubt the presence of some monoepoxide. In any event, to determine from molecular weight and hydroxyl value, a whole series of compounds has been made using this etc., it corresponds approximately to the following comparticular cogeneric mixture and assuming the molecular position: 40 weight to be 462. The color and physical appearance of the products were substantially the same as in the --where i 0 Z;Zf Z, 1 case of Table III. The xylene solubility Was at least as 8% where is 2 good as the corresponding compounds in Table III and 5% where is 3 the solubility in acetic acid was usually no better than,

t and perhaps not quite as good as the corresponding 'prod- The average molecular weight is 460 compared to 340 nets in Table III. The data is again summarized for for the monomer (where n 1s 0). However, the fact convenience in Table IV, following.

TABLE IV Molar Time of Max. v Ex. Reactants ratio r temx, Color and physical state Solubility No. (hrs) H 0-insoluble. E1--- Trlethanolamine, 149.2 g. +31, 231 g 2:1 6 142 Brownish semi-solid {5% acetic acid-soluble.

Xylene-soluble.

HaO-insoluble. E2 Triisopropanolamine, 94 g.+B1, 116g 2:1 8.5 183 .do 5% acetic acid-soluble. V v Xylene-soluble.

HzO-insoluble. 153-..- Dihydroxyethylethylenediemine,73g.+B1,116g.- 2:1 10 102 Brown semi-solid 5% acetic acid-soluble.

Xy1eneinsoluble.

. Bio-insoluble. 1 14---. Aniline,93g.+B1,231g 2:1 5 94, Dark amber almost hard solid.-- @fffiggfififi Xylene+CH=OH-solubie.

5 9 ti i d lnsol bl 806 08C l1 0. 1 15---- Phenylethanolamine, 137 g.+B1, 231 g 2.1 4. 5 93 Yellow brittle solid X1ene ins0]ub1e I yeng|-CH;OH-soluble.

'- S l1 6. D6 Phenyldiethanolamine, 90.5 g.+B1, 116g 2:1 5 179 Dark amber viscous liquid 5% acetic acid-insoluble.

Xylene-soluble. Ego-insoluble. 117--.- Ethylphenylethanolamine, 62.5 g.+B1, 88 g 2:1 14 152 Amber liquid 5% acetic acid-insoluble.

Xylene-soluble. Bio-insoluble. 158-..- Diphenylamine, 84.6 g.+'.B1, 116 g 2:1 7 191 Brown liquid 5% amtic acid-insoluble.

Xylene-soluble. HzO-insoluble. 159...- Morpholine, 87 g.+B1, 231 g 2:1 7 Amber solid mass 5% acetic acid-soluble.

Xylene-soluble.

-See footnotes at end of table.

TABLE IVContinued* Ex. N 0.

Reactants Molar:

ratio Time '0! reaction Max.-

Color and physical state Solubility 1,3-dimethylurea, 88.1 g.+B1, 231 g Di-2-ethylhexyl ethanolamine, 142.5 g.+B1, 116 g-- Triethanolamine-i-urea 1:4, +100 g.+B1, 92.5 g..

Triethanolamine+propy1ene oxide 1:3,

g.+B1, 116 g.

Tr1ifhanolamine+ethylene oxide 1:3, 140.5 g.+B1,

Trlifhanolamine+ethylene oxide 1: 6, 206.5 g.+B1,

Triethanolamine+propy1ene oxide 248.5

1:6, g.+B1, 116 g.

Tziilehanolamine+ethylene Oxide 1:9, 272.5-l-B1 Triethanolamine+propylene oxide 1:9, 268.4 g.+

2-Aminopyridine, 94 g.+B1, 231 g N-methyl aniline, 53.5 g.+B1, 116 g N-ethyl aniline, 60.6 g.+B1, 116 g Ethyldiethanolamiue, 68.5 g.+B1, 116 g.

Butyldiethanolamine, 82.5 g.+B1, 116 g Benzylamine, 53.6 g.+B1, 116 g- 2-amino-4-methyl pentane, 50.5 g.+B1, 116 g 2-amino-2-ethyl 1,3-propanediol, 66.5 g.+B1, 116 g.

z-ziilnirgio-z-methyl 1,3-propanediol, 54.5 g.+B1,

Diamylamine, 78.7 g.+B1, 116 g N onylamine, 71.7 g.+B1, 116 g Di-zethylhexylamine, 120.5 g.+B1,- 116 g Furfurylamlne, 97 g.+B1, 231 g:

See footnotes at end of table.

Amber solid Amber almost hard mass Dark amber thick liquid Brownish almost hard mass Red thick liquid Amber viscous liquid Amber viscous mass Brown almost hard solid Brown viscous liquid Black hard mass Yellowish viscous liquid Brownish semi-solid Brown viscous mass.

Thick brown liquid Amber solid Dark amber solid Amber solid Amber thick liquid Amber viscous mass Amber thick liquid Dark amber mass;

5% acetic acidinso1uble.' Xylene-insoluble. CHaOH-soluble. {Hm-insoluble.

{EGO-insoluble.

5% acetic acid-dispersible. Xy1enesolub1e (hot). Ego-insoluble. 5% acetic acid-dispersible. Xylene-soluble. Ego-insoluble. 5% acetic aciddispersible. Xyleneso1uble. HzO-insoluble. 5% acetic acid-soluble. Xylenesoluble. Hz0inso1ub1e. 5% acetic acidsoluble. XyIene-soluble. H2O111S0lllbl8. 5% acetic acid-soluble. Xylene-solub1e. HzO-insoluble. 5% acetic acid-dispersible. Xylene-soluble. HzO-insoluble. 5% acetic acid--dispersible. Xylene-solub1e. HzO-insoluble. 5% acetic acid-insoluble. Xylene-insoluble. CHsOHsoluble. HaO-insoluble. 5% acetic acid-soluble. Xylene-insoluble. Xy1ene+OHz0H-Soluble. Hz0-soluble. 5% Acetic acid-soluble. Xy1ene-inso1ubie. Xylene-i-CHsOH-SOluble. HzO-soluble. 5% acetic acidso1uble. Xyleneinso1uble. Xylene+CHaOH-solub1e. HzO-insoluble. v 5% acetic acid-soluble. Xylene-partly soluble. Xylene-l-CEIaOH-soluble.

H;OSolu 1e. 5% aceticacid-soluble.

Xylene-msoluble.

ylcne-l-OHaOH-soluble.

Xylene-partly soluble.

Xylene+OHaOH-soluble.

HzO-insoluble.

Xylene-insoluble.

CH OH-soluble.

5% acetic acid-insolub1e.

ylene-soluble.

EEO-insoluble.

5% acetic acid-insoluble.

Xylene-soluble.

5% alctetic acid-soluble (diific Xylene-partly soluble.

ylene-l-OHzOH-soluble.

Bio-insoluble. 5% acetic acid-soluble.

Xylene-partly soluble.

ylene+OHaOH-solub1c.

E o-insoluble.

5% acetic acid-d1spersible.

Xylcnepartly soluble.

ylene+OHaOH-so1uble.

5% acetic acid-dispersible.

yleue-soluble.

E o-insoluble.

5% acetic acid-soluble.

Xylene-insoluble.

yle11e+OHaOH-S0lubl9.

H20-insoluble.

5% acetic acid-soluble.

Xylene-insoluble.

E o-insoluble.

5% acetic acid-insoluble.

ylenes luble.

EEO-insoluble.

5% acetic acid-insoluble.

ylene-snluble.

E o-insoluble.

5% acetic acid-insoluble.

ylcne-sfllublc.

5% acetic acid-dxsgiersible.

ylene-solublcV Ex. No.

Reactants Molar ratio Time of react inn Max.

te mis,

Color and physical state Solubility Ethylene diamine, g.+B1, 231 g Propylene diamine, 74 g.+B1, 231 g p-Phenylene diamine, 54 g.+B1, 116 g Diethylene triamine, 103.2 g.+B1, 231 g Tetraethylene pentamine, 94.7 g.+B1, 116 g Tetraethanol tetraethylene pentamine, 182.7 g.+

As to nitrogen compound. See Note 1, 141.6 g.+

Aslgo nitrogen compound. See Note 2, 206 g.+B1,

Triethanolamine-l-propylene oxide 1:12, 169 g.+

Trietheno1amine+ethylene oxide 1:12, 135.4 g.+

Triethanolamine+propylene oxide 1:18, 238.6 g.+

Triethanolamine+ethylene oxide 1:18, 188.2 g.+

Triethanolamine+propyiene oxide 1:15, 203.8 g.+

Triethanolamine-l-ethylene oxide 1:15, 161.8 g.+

Decylamine 10D, 78.5 g.+B1, 115 g Dodecylamine 12D, 92.5 g.+ B1, 115 g Hexadecylamine 16D, 122 g.+B1, 115 g Octadecylamine 18D, 133.5 g.+B1, 115 g p-Aminophenol, 54.5 g.+B1, 115 g Beta-phenyl ethylamine, 60.5 g.+B1, 115 g Benzene sulfonyl ethylamide, 92.6 g.+B1, 115 g Benzene sulfonyl isopropylamide, 99.6 g.+B1,

Benzene sulionamide, 78.6 g.+B1, 115 g p-Toluene suifonyiethyl amide, 99.7 g.+B1, 115 g..

Armid 10, 86 g.+B1, 115 g Armid 14," 57 g.+B1, 58 g Armid 16, 64.5 g.+Bl, 58 g Triethanolamine+propylene oxide 1220.5, 133.8 g.

+Bl, 23 g.

Triethanolamine-l-propylene oxide 1:27, 171.5 g.

See footnotes at end of table.

Amber viscous mass Dark brittlesolid Dark amber mass Amber hard mass Darkish brown almost hard mass.

Dark amber hard mass Viscous yellow liquid Viscous brown liquid Viscous amber liquid Dark amber viscous liquid Dark amber thlck liquid Amber mass Almost black solid Brownish viscous mass Dark brown solid mass Yellow viscous liquid Dark amber mass Amber solid Reddish brown liquid.

H 0-insoluble.

5% acetic acid-soluble. Xylene-insoluble. Xylene+CH3OH-so1uble. EEO-insoluble.

5% acetic acid-soluble. Xyleneinsoluble Xylene+CH:;OH-soluble. Ego-insoluble.

5% acetic acid-soluble. Xylene-insoluble. Xylene+CH;0H-soluble. HzO-dispersiblc.

5% acetic acid-soluble. Xylene-dispersible. Xylene+OHaOH-soluble EEO-dispersible.

5% acetic acidsolub1e. Xylene-dispersible. Xylene+CH3OH--solublc.

HzOd1Spe!S1h16.

5% acetic acid-soluble. Xylene-dispersible. Xylene+CH OHso1uble.

HzO-insoluble. 5% acetic acidsoluble. Xylene-soluble.

5% acetic acidsoluble. Xylenes0luble.

5% acetic acid-soluble. Xylene-soluble.

Xylene-partly soluble.

yiene-i-OlEhOH-soluble.

Ego-soluble. 5% acetic acid-soluble.

5% acetic acid-soluble. Xylene-soluble.

{Bio-insoluble.

Ego-soluble. 5% aceticacidsolub1e. Xylene-soluble but cloudy.

ylene+CHzOH-soluble.

5% acetic acid-soluble.

ylene-soluble.

{ZN-dispersible.

Xyleneso1ublc (cloudy).

ylcne+CHaOHsoluble.

HzO-soluble. 5% acetic acid-soluble.

5% acetic acid-insoluble. Xylene-soluble.

{Ibo-insoluble.

5% acetic acid-insoluble.

Xylene-soluble.

EEO-insoluble.

5% acetic acid-insoluble.

ylene-soluble.

Ego-insoluble.

5% acetic acid-insoluble.

ylcnesoluble.

H O- soluble.

5% acetic acid soluble.

Xxlencinsoluble.

yleue+CHaOH-soluble.

HaO-insoluble.

5% acetic acid-insoluble.

ylene-soluble.

HaO-insoluble.

5% acetic acid-insoluble.

ylene-slluble.

Ego-insoluble.

5% acetic acidinsoluble.

ylene-soluble.

{Ego-insoluble.

5% acetic acidinsolubie.

Xylene-insoluble.

Xylene+CHzOHsoluble.

E O-insoluble.

5% acetic acid-insoluble.

ylene-soluble.

{Ego-insoluble.

5% acetic acid-insoluble. Xyleneinsoluble. Xylene+OH;OH-soluble. HzO-insoluble. 5% acetic acid-insoluble. Xylene-insoluble.

ylene+CH3OH-s0luble. HzO-insoluble. I 5% acetic acidinsoluble. Xyleneinsoluble.

ylene+OH;0H-soluble. Ha0-insoluble. 5% acetic acid-soluble.

ylene-soluble. EEO-insoluble. 5% acetic acidsoiub1e.

ylene-soluble.

{E o-insoluble.

TABLE Iii-Continued Molar Time of Max. Ex. Reactants ratio reaction temp., Color and physical state Solubility No. (hrs.) O.

HnO-insoluble. E6S Tricthanolamine+propylene oxide 1:302, 190 g. 2:1 4.5 178 Reddish brown liquid. 5% acetic acid-soluble.

+ 1, 23 g. Xylenesluble.

EyzG-salubled 1 bl 0 ace c 9.01 -sou e. E69 Trietlialgglammc+ethylene oxide 1.21.2, 108.2 g. 2.1 4.5 188 do Xy1ene+a1coho1 1:1

- soluble.

H 7gO-stolubliei 1 b1 1 a ace ac so u e. E70 Trrethanolamme-I-ethylene oxide 1.24.3, 121.8 2.1 4.5 178 do Xy1ene+a1cohol (1:1

g.+B1, 23 g.

soluble. g/5O s1ub]ed 1 b1 0 ace 10 2.01 -so u e. E71 Tuetligilogmme-l-ethylene oxide 1.26.9, 133.3 2.1 4.5 182 .do Xy1ene+a1coh01 (1:1 mix) soluble.

7 t 1 1 bl ace cac1 sou e. E;2 Tr1i=ihanolan1ine+eth lene oxide 1.33.8, 163.6 2.1 4.5 183 .do Xy1ene+a10oh0l (1:1 mix) g. B1, 23 g.

soluble. H2O-i11S01l1b16. E73 Furfurylamine-i-propylene oxide 1:17.9, 113.5 2:1 .20 173 --do 5% acetic acid-dispersiblc.

g.+B1, 23 g. Xylene-soluble.

HzO-1I1S0111b16. E74 Furfurylamine+propylene oxide 1:21, 131.5 2:1 2.0 162 do 6% acetic acid-dispersible.

g.+B1, 23 g. Xylenesoluble.

H2O- insoluble. E75 Furfury1amine+propy1ene oxide 1:24, 148.9 2:1 2.0 178 .do 5% acetic acid-dispersiblo.

g.+B1, 23 g. Xylene-solu 9.

H1O- insoluble. E76." Furfurylamine+propylene oxide 1:265, 163.4 2:1 20 190 do 5% acetic acid-dispersible.

g.+B1, 23 g. Xylene-soluble.

E o-insoluble. E77 Furfurylamine+pr0py1cne oxide 1:305, 186.6 2:1 1.0 177 -do 5% acetic acid-disperslble.

g.+B1, 23 g. Xylene-soluble.

Ego-insoluble. E7s Furfurylamine-E-propylene oxide 1251.8, 2:1 1.0 182 Reddish liquid 5% acetic acid-dispersible.

g.+B1, 12.2 g. Xylene-soluble.

2% sodium methylate used as catalyst. See previous reference to this material.

NOTE 1.-Obta.1ned b diamine.

NOTE 2.0btained by reaction from 1 mole amylphenolresin, 2 moles formaldehyde, and 2 moles diethanolamine.

TABLE V y reaction from 2 moles butylphenoLZ moles formaldehyde, and 1 mole dihydroxyethyl, ethylene- Example Number CnHi H OH E cu aool CiaHmOaS (M. W. 362).

(13.-.. Furl'urylamine, 97 g.+F1, 149 g 2:1

Previous attention has been directed to the fact that the diglycidyl ethers may not have any bridge connecting the aromatic nuclei, or the bridge may be derived from sulfur dichloride, from an aldehyde and particularly formaldehyde, or maybe the residue of a sulfonic acid, i. e., a sulfone radical. There is no advantage in using these particular compounds as far as we have been able to determine and thus our preference has been to employ compounds where the bridge is derived from a ketone and particularly acetone, due in part to commercial availability. We have attempted to prepare comparatively technically pure compounds corresponding to some previously noted and which appear for convenience again in Table VI immediately following. The method of preparati'on, of course, is obvious in light of what has been said previously, or what has been described elsewhere in the literature.

As has been pointed out previously, our preference is to use compounds having at least one basic nitrogen and in many cases a repetitious ether linkage obtained by oxyalkylation. The following derivatives were obtained in the same manner as described previously in connection with diglycidyl 'ethers where the bridge between the phenolic nuclei happened to be, in cost cases, from a kctone.

36 For reasons which are obvious in light of what has been said previously, the majority of examples, in fact all prior examples, are concerned with instances where the ratio of the amine reactant to the polyepoxide is two-to-one. One reason is that the epoxide is usually the most expensive reactant and, everything else being equal, one attempts to obtain the best results with the least amount of the more,

or most expensive, reactant. This ratio need not be employed. Other obvious ratios can be used; for instance,

one may use a ratio of one-to-one, provided, of course,

that the amine preferably has at least two reactive hydrogen atoms. If the amine does not have at least two reactive hydrogen atoms, one mole of the epoxide may react and make available a new labile hydrogen atom which is then susceptible to further reaction. On the other hand,

soluble, or semi-insoluble mass suggestive of gelation or incipient thermosetting action, or one may even obtain a hard type of resin suitable only for purposes other than those herein described and perhaps be useless for any purpose.

TABLE VI N o. I Reactants ratio Color and physical state Solubility G1... Tricthanolamine, 149.2 g. +F1, 149 g 2:1

G2 Tri-isopropanolaminc,94 g.+F1, 74.5 g 211 (14.--- Triethauolamine ethylene oxide 1:18, 188.2 g. 2:1

(15.... Furiurylamine propylene oxide 1:17.9, 113.5 2:1

g.+F1, 14.9 g.

G6..-. Triethariolarnine, 74.6 g.+132, 117.5 g 2:1

67.... Tri-isopropanolaminc, 94 g.+F2, 117.5 g I 2:1

(38.. Furiurylamine, 97 g.+1*2, 235 g 2:1

(39.--. Triethanolamine ethylene oxide 1:18, 188.2 2:1

G14... Triethanolamine ethylene oxide 1:18, 188.2 2:1

g.+F3, 59.2 g.

G15... Furfurylamine propylene oxide 1:17.9, 113.5 2:1

g.+F3, 29.6 g.

G16..- Triethanolamine, 149.2 g.+I"4, 181 g 2:1

G17.-. Trl-isopropanolamine, 9-4 g.+1*4, 90.5 g 2:1

G18... Furturylamine, 97 g.+F4, 181 g 2:1

G19.-. Triethanolamine ethylene oxide 1:18, 188.2 2:1

g.+F4, 36.2 g.

G20--- Furturylamine propylene oxide 1:179, 113.5 2:1

g.+F4, 18.1 g.

HzO-iusoluble. Brown semisolid. 5% acetic acidso1uble.

, Xy1enesoluble 1 Hz soluble. 185 do 5% acetic acid-soluble.

Xylene-soluble. HzO-insoluble. 5% acetic acid-uispersiblc. Xylenesoluble.

{HzO-soluble.

180 Dark brown semisolid 5% acetic acidsoluble. Xylene-soluble (cloudy). Xylene OH3OHsolublc. {Ego-insoluble.

Dark brown thick liquid 170 ....do 5% acetic acidso1ublc.

Xylenesolub1e. HzO-insoluble.

140 Dark semisolid 5% acetic acid-soluble.

Xylene-soluble. H20i11$0l11b18. 5% acetic acidso1uble. Xylenesolublc; Ego-insoluble. 5% acetic aciddispersib1c. Xylene-soluble.

5% acetic acid-soluble.

Xylencsoluble (cloudy).

Xylene CH3OHsolublc.

165 -do 5% acetic acid-soluble.

Xylene-soluble.

HaQ-iusoluble.

140- Dark semisolid 5% acetic acid-soluble.

Xylene-soluble.

150 do 5% acetic acid-soluble.

{Hz0insoluble.

150 Dark thick liquid 165 do 5% acetic aciddispersible.

Xylene-soluble. H O-diSQBISlblG.

5% acetic acid-soluble. Xylene-soluble (cloudy). Xylene CHaOH-solublc. Hr0insoluble.

5% acetic acidsolublc (hot). Xylene-soluble. {E o-insoluble.

150 Dark thick liquid 150 Dark semisolid 5% acetic acid-soluble.

Xylenesolublc.

do 5% acetic acid-soluble.

Xylenesoluble.

Hz0insoluble.

5% acetic acid-dispersible. Xylene-soluble. H2Osoluble.

5% acetic acid-soluble. Xylenesoluble (cloudy). Xylene CHaOH-soluble. {Hm-insoluble.

160 Dark thick liquid 165 -do 5% acetic acid--soluble.

Xylene-so1uble.

Notein the table following, i. e., Table VII, the materials obtained in the manner described in this table use a molal ratio of one-to-one. The reaction masses become semi-resinous and give solutions which usually are either almost insoluble in water, or are dispersible to a modest degree at least, but which are somewhat more dispersible in dilute acid. They are also soluble or dispersible as a rule in xylene or a mixture of xylene and methyl alcohol (one-to-one). The products obtained were comparatively thick liquids and indicated that the molecular size was considerably higher in proportion than comparable compounds obtained by the tWo-to-one ratio. Such materials tend in the direction of potential insolubility and are particularly desirable for the reason that they adsorb rapidly at the interface. Likewise, when B on Example J] The oxyalkylation-susceptible compound employed was the resin previously described as Example E1. Example E1, in turn, was obtained from triethanolamine and Example Bl as described in Table II. The autoclave employed in this particular instance was approximately 5 gallons in size. In other instances somewhat larger autoclaves have been used, for instance, 10, or gallon sizes. However, this is immaterial. 8.5 pounds of oxyalkylationsusceptible compound El were placed in the autoclave along with an equal amount of solvent. In this series of examples the solvent employed was Xylene. This applies to the series appearing in subsequent Table VIII with the exception that the series derived from oxy- 15 converted into new compounds by oxyethylafion alkylation-susceptible compound E3 used as a solvent a propylation, acylation, or similar processes, the resultant *50 mlxture of Xylene dlefl'lyleneglycol (1161111371 of reaction has these same properties to an equal or ether- The amount of Catalyst used y Powdered greater degree. caustic soda) was .8 pound. Ad ustment was made to TABLE VII Ex. Molar Time of Max. No. Reaetants ratio razfictign te mop Color and physical state Solubuity 5H2Oitr lsolu ble.d H1 Triethanolamine-I-propylene I oxide 1:18, 119.3 1:1 1.5 150 e o thick liqui gffi fgfiga i f gi g? g.+3A, 34 g. sible.

5H2O-i1 solubdle.d b1 n2. Ftirfgrylamine-l-propyleneoxide1251.8,155g.+3A, 1:1 1.0 150 rown hick liq i g gf jfgg g fi ffi f j- Hz0-insolu tle.d H3 Furlfurylamine-kpropyleneoxide1:66.23,199g.+3A, 1:1 2.0 165 Yellow hick liqui g g gg gp gqggg ge si e.

D k] d E/zO-disperaiblel b1 114.. Furiur -lamina ethylene oxide propylene oxide 1:1 2.0 air 1qu1 a acetic aei so u e,

1115.5:9, 130 gi l-3A, 34 g. Xy1ene+OHsOHsoluble.

v Hz01ns0lu ble. H5 Triethylene tetramine+propylene oxide 1:12, 41.3 1:1 1. 0 rO Sh thick llquld 5% acetic aeiddispersible. g.+3A, 17 g. Xylene+CHaOHsoluble.

Y 11 th 1:1 (1 {5 7 t i 'd b1 P -d' ylene oxide 1210.3 67 1:1 1.5 135 0 ic iqui ace ic aci ispersi 0. H6 2 1 5 Emma-Twp g+ Xlene+CHaOH-soluble.

1) kb n1 kl d y t ii 'd bl \l t.- h l he d mine ro lene oxide 1:27.6 1:1 1.5 ar rown ic iqui ace ic aci ispersi e. H7 1 351 345 3 1: 17 g +p Dy XI16HQ+CHzOH-S01l1ble.

B th kl d E l 7 i d d bl D h I 1; am 0 lene oxide 1:18.7 59.4 1:1 1.5 130 ro n i0 iqui ace ie not ispersi e. H8 57 me+pr Dy iX1ene+CHaOH-soluble.

H2O-d isper sible. H9 Furiurylamine+ethylene oxide-{propylene oxide 1:1 .5 100 do 5% acetic ae1dsoluble.

1:15.5:11.3, 143.4 g.+3A, 34 g. Xylene soluble.

HzO-drspersrble. H10-.. Furiurylamine+ethyleue oxide+propylene oxide 1:1 1 100 do 5% acetic ao1d-soluble.

1:15.5:16.4, 173 g.+3A, 34 g. Xylene-soluble.

H2Odisper slble. H1l Furfurylamine+ethylene oxide-{propylene oxide 1:1 1 100 .do 5% acetic acid-soluble.

1:15.5:23.5, 214.2 g.+3A, 34 g. Xylene soluble.

H2Od sper s1ble. H12--. Furfurylamine+ethylene oxide+propyle11e oxide 1:1 1 100 .r d0 5% acetic acidsoluble.

1:15.5:32.2, 264.6 g.+3A, 34 g. Xylenesoluble.

PART 6 The preparation of the compounds or products described in Part 5, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxy alkylation step but involves the use of a monoepoxide or the equivalent. The principal difierence is only that while polyepoxides are invariably nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glycide and methylglycide react under practically the same conditions as the polyepoxides. Actually, for purpose of convenience, it is most desirable to conduct the previous reaction, i. e., the one involving the polyepoxide, in equipment such that subsequent reaction with monoepoxides may follow without interruption. For this reason considerable is said in detail as to oxyethylation, etc.

As the oxyalkylation procedure is substantially con ventional, and carried out in equipment of the type commonly used for oxyalkylation, the procedure will simply be illustrated by the following examples:

operate the autoclave at approximately C. In some other instances higher temperatures were employed, up to C. or C. or C. Adjustment was made also to operate at a pressure not in excess of 30 pounds per square inch. The time regulator was set so as to inject 8.5 pounds of ethylene oxide slowly over a one-hour period. The reaction Went readily and, as a matter of fact, the oxide was taken up probably in considerably less than this time. The speed of reaction, particularly at the comparatively low pressure, undoubtedly was due in a large measure to effective agitation and also to the comparatively high concentration of catalyst. The theoretical molecular weight at the end of the reaction was 1700. The molal ratio of ethylene oxide to oxyalkylation-susceptible compound (i. e., the initial resin) was 19.25 to 1.

Example J2 This example illustrates further oxyalkylation of Example J l, preceding. The oxyalkylation-susceptible compound, to wit, E1, is the same as was used in Example 11, because it was merely a continuation. In subsequent examples, such as for example listed in Table VIII, the oxyalkylation-susceptible compound shown in the horizontal line concerned with Example J2 refers to oxyalkylation-susoeptible compound E1. Actually, one could refer just as properly to Example J1 at this stage. It is immaterial which designation is used so long as its use is practiced consistently throughout the tables. In any event, the amount of ethylene oxide used is the same as before, to wit, 8.5 pounds. This means the oxide at the end was 17 pounds. Similarly, the ratio of ethylene oxide to oxyalkylation-susceptible compound (molar basis) at the end was 38.5 to 1. The theoretical molecular weight was 2544. There was no added solvent. Similarly, there was no added catalyst. The time period was slightly more than one hour, to wit, 1 /2 hours.

In all succeeding examples the temperature and pressure were the same as previously, to wit, 125 C. to 130 C., and not over 15 pounds per square inch. The time element varied somewhat as noted in succeeding xamples.

Example J3 The oxyethylation proceeded in the same manner as described in Example 11 and I2, preceding. There was no added solvent and no added catalyst. The oxide added was one-half of the previous amount, to wit, 4.25 pounds. The total oxide at the end of the oxyalkylation procedure was 21.25 pounds. The molal ratio of oxide to condensate was 48 to l. The theoretical molecular weight was 2970. As noted previously, the conditions in regard to temperature and pressure were the same as in regard to Examples 115 and 2b. The time period was a little shorter than before, to wit, hour.

Example J4 The oxyethylation was continued and the amount of oxide added was the same as before, to wit, 4.25 pounds. The amount of oxide added at the end of the reaction was 25.5 pounds. There was no added solvent and no added catalyst. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was one hour. The molal ratio of oxide to oxyalkylation-snsceptible compound was 57.8 to 1. The theoretical molecular weight was 3390.

Example J5 The oxyethylation was continued with the addition of another 4.25 pounds of oxide. N0 added solvent was introduced and likewise no added catalyst was introduced. The theoretical molecular weight at the end of the reaction was 3812. The molal ratio of oxide to oxyalkylation-susceptible compound was 67.5 to 1. The time period was one hour. The total amount of oxide at the end of the period was 29.75.

Example J6 The oxyalkylation was continued with the addition of the same amount of oxide as before (4.25 pounds). There was no added solvent and no added catalyst. The amount of oxide in at the end of the reaction period was 34 pounds. The theoretical molecular weight was 4230 and the ratio of oxide to oxyalkylation-susceptible compound was 77 to l. The time period Was a little longer than previously, to wit, 1 /2 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensations described previously. All these data have been presented in tabular form in Tables VIII through X.

In substantially every case a 35-gallon autoclave, was employed, although in some instances the initial oxyethylation was started in a -gallon autoclave and then transferred to a -gallon autoclave, or at times to the -gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring to'Tables VIII, IX, and X, it will be noted that compounds 11 through J18 were obtained by the use of ethylene oxide, whereas Examples 119 through 136 were obtained by the use of propylene oxide; and Examples J37 through 154 were obtained by the use of butylene oxide.

Referring now to Table IX specifically, it will be noted that the series of examples beginning with K1 were obtained, in turn, by use of both ethylene and propylene oxides, using ethylene first; in fact, using Examples J4 as the oxyalkylation-susceptible compound in the first 6 examples. This aplies to series K1 through K18.

Similarly, series K19 through. K34 involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, K19 was prepared from 124, a compound which was initially derived by use of propylene oxide.

Similarly, Examples K37 through K54 involve the use of ethyleine oxide and butylene oxide, the ethylene oxide being used first. Also, these two oxides were used in the series K55 through K72, but in this latter instance the butylene oxide was used first and then the ethylene oxide.

Series K73 through K involve the use of propylene oxide and butylene oxide, butylene oxide being used first and propylene oxide being used next.

In series L1 through L18 the three oxides were used. It will be noted in Example L1 the initial compound was K78; Example K78, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide aded in the series L1 through L6 was by use of ethylene oxide as indicated in Table X.

Referring to Table X, in regard to Example L19 it will be noted again that the three oxides were used and L19 was obtained from K57. Example K57, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example L19 and subsequent examples, such as L20, L21, etc., propylene oxide was added.

Tables XI, XII, XIII give the data in regard to the oxyalkylation procedure as far as temperature and pressure are concerned and also give some data as to solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referring to Table VIII in greater detail, the data are as follows: The first column gives the example numbers, such as J 1, J2, J3, etc. etc.; the second column gives the oxyalkylation-susceptible compound employed which, as previously noted in the series J1 through I 6, is Example El, although it would be just as proper to say that in the case of J2 the oxyalkylation-susceptible compound was J1, and in the case of J 3 the oxyalkylation-susceptible compound was 12. Actually, reference is to the parent derivative for the reason that the figure stands constant and probably leads to a more convenient presentation. Thus, the third column indicates the epoxide-derived condensate previously referred to.

The fourth column shows the amount of ethylene oxide in the mixture prior to the particular oxyethylation step. In the case of Example I1 there is no oxide used but it appears, of course, in I2, 13, and I4, etc.

The fifth column can be ignored for the reason that it is concerned with propylene oxide only, and the sixth column can be ignored for the reason that it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powdered caustic soda. The quantity used is shown.

The eighth column shows the amount of solvent which is xylene unless otherwise stated.

The ninth column shows the oxyalkylation-susceptible compound which in this series is a polyepoxide-derived nitrogen compound. 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER; SAID DEMULSIFIER BEING OBTAINED BY A TWO-STEP MANUFACTURING METHOD CONSISTING OF FIRST REACTING (A) A MONOMERIC NON-RESINOUS NITROGENCONTAINING COMPOUND CONTAINING AT LEAST ONE NITROGEN ATOM SELECTED FROM THE CLASS CONSISTING OF AMINO AND AMIDO NITROGEN ATOMS AND CONTAINING AT LEAST ONE ACTIVE HYDROGEN ATOM, AND (B) A PHENOLIC POLYEPOXIDE FREE FROM REACTIVE FUNCTIONAL GROUPS OTHER THAN EPOXY AND HYDROXYL GROUPS, AND COGENERICALLY ASSOCIATED COMPOUNDS FORMED IN THE PREPARATION OF SAID POLYEPOXIDES; SAID EPOXIDES BEING MONOMERS AND LOW MOLAL POLYMERS NOT EXCEEDING THE TETRAMERS; AND EPOXIDES BEING SELECTED FROM THE CLASS CONSISTING OF (A) COMPOUNDS WHERE THE PHENOLIC NUCLEI ARE DIRECTLY JOINED WITHOUT AN INTERVENING BRIDGE RADICAL, AND (B) COMPOUNDS CONTAINING A RADICAL IN WHICH TWO PHENOLIC NUCLEI ARE JOINED BY A DIVALENT RADICAL SELECTED FROM THE CLASS CONSISTING OF KETONE RESIDUES FORMED BY THE ELIMINATION OF THE KETONIC OXYGEN ATOM, AND ALDEHYDE RESIDUES OBTAINED BY THE ELIMINATION OF THE ALDEHYDE OXYGEN ATOM, THE DIVALENT RADICAL 